Animalizing textile product



Feb- .18, 1941. P. EssELMANN ET Al. 2,231,892

ANIMALIZING TEXTILE PRODUCT FiledJuly 13, 1939 l NVENTORS Pett/,4. fssel. gfmwv y Patented Feb. 18, 1941 YUNITED STATES PATENT OFFICE ANIMALIZING TEXTHLE PRODUCT New York, N. Y.

Application July 13, 1939, Serial No. 284,245

In Germany August 4, 1937 2 4 claims.

This invention relates to a process of producing artificial fibers, films, foils, ribbons and the like materials capable of being dyed by acid wool dyestuis.

In our prior application Ser. No. 223,010 filed August 4, 1938, of which the present application is a continuation in part, we have disclosed a method of animalizing artificial fibers by incorporating therein the product of the joint polymei-ization of an alkylene imine and an arylisocyanate or arylisothiocyanate.

In a prior application filed by us together with arl Ksslinger, Ser. No. 182,250 we have disclosed animalizlng of textile materials by incorporating therein resinous condensation or polymerization products of carbon disulde and ethyleneimine.

In our co-pending application of even date Ser. No. 284,244 filed July 13, 1939 we have disclosed a new type of synthetic resins which are derived from alkylene imines, carbon disulfide and arylisocyanates or arylisothiocyanates by joint polymerizat-ion.

`It is an object of the present invention to provide a process by which artificial textile materials capable iof being dyed with acid wool dyestuils in the same manner as wool may be obtained.

A further object is the provisionof artificial bers, threads and the like textile materials, which consist of cellulose hydrate, cellulose acetate or a similar iilmor fiber-forming polymer and which contain dispersed therein anaddition of a basic artificial resin.

A further object resides in the provision of artistuffs with a fastness to light and washing, which equals that of wool and which exceeds that of all 2 the animalized fibers hitherto in use.

Still further objects of the invention will become apparent from thedetailed speciiication tollowing hereinafter. The single ilgure illustrates a fabric of a conventional formwlth legends to indicate the ima provement of this invention.

We have now found that improved animalizing agents are obtained by jointly polymerizing carbon disulfide or any of the above-named substituents therefor, a cyclic imine and 'an aromatic isocyanate or an isothiocyanate.

As cyclic imines the following polymerizable imines having a three-membered ring are named.

as examples: ethylene imine, N-methylethylene imine, N-phenylethyleneimine. propyleneimine, N propylethyleneimine, N benzylethyleneimine,

' ncial obers, which may be dyed by acid woo1 dye- Y butyleneimine, and polymers of these-alkyleneimines.

As isocyanates phenylisocyanate may be mentioned, further phenylisothiocyanate, benzylisocyanate, naphthylisocyanate and. thecorrespond- 5 ing isothiocyanates. I

The proportions of the constituents of the resin may vary within wide limits. There should be present at least 5 per cent as the smallest addition of one component and not more than per cent of the single further component, for instance 10 to 50 per cent of arbon disulfide of the weight of the two other resin components may be present.

The polymerization is preferably carried out as |r, follows: carbon disulde or carbonyl sulfide or thiophosgene or sulfur chloride is added drop by drop to a solution of the alkyleneimine. The temperature during this reaction should not rise about to 100 C. since in that case the reaction products are no longer uniform. The preferred temperature is around 40 to 50 C. 'I'he polymerizate obtained from the sulfur compound and the alkyleneimine is allowed to stand for a certain period which may be a few hours or a couple of days. This condensationor polymerization product is then reacted with an arylisocyanate preferably in an amount that the resultant solution is neutral. 'I'he solution obtained polymerizes spontaneously by standing for a certain time. However, the polymerization may be accelerated by acid or basic catalysts or by heating. vProducts of high degree of polymerization are obtained by heating the resin for -a longer period after it has been separated from the solution. Alternatively carbon disulilde may be rst'condensed with phenylisocyanate and then the ethyleneimine added to complete the polymerization;

'I'he resins according to this invention have a distinctly basic character. They are stable against acid'and alkaline liquids and absorb acid dyestuifs eagerly. 2

We have .found that these products are especially useful for animalizing textile materials which are per se incapable of being dyed by acid dyes in the same' manner as animal bers. ('Ihe term ,animalizing" means imparting to vegetable and artificial fibers such as cotton and rayon the dyeing properties of animal ilbers such as wool and silk. For the use of this term compare Brit- 5o j ish Patents Nos. 501,595, 501,804, and 493.509.) The process is carried outby incorporating the insoluble reslnous compositions in the spinning solutions in finely subdivided form for instance in the form of an emulsion and spinning the libera from this solution. However, it is also possible to impresnate textile fibers such as cotton with a solution of the resins, pressing and drying the same. The incorporation into the spinning solution is preferably carried out as follows: The resin is dissolved in a solvent therefor and this solution is added to the spinning solution for instance to a viscose solution. Preferably solvents are selected which are immiscible with the solvent of the fiber-forming polymer so that the resinous solution can be emulsifled in .the spinning solution. 'I'his may be facilitated with the aid of emulsifying agents.

In the case of solutions of organic polymers in organic solvents the anlmallzing agent may be dissolved in the organic solvent for the ilberforming polymer or it may be emulsifled inthe spinning solution as above.

'I'he following solutions of liber-forming polymers which are suited for the production of animalizedibers may lie/mentioned by way of example: viscose solutions, cuprammonia cellulose solutions, cellulose ester solutions, cellulose ether solutions, solutions of vinyl resins.

As already pointed out the artificial ilbers 'or the cotton fibers may be impregnated with the animalizing agent in the form of illaments, yarns, threads, fabrics, etc. After drying such textiles contain a certain amount of the polymerization products according to the invention and acquire exactly the same aillnity towards wool dyestuils and chrome dyestuils as wool. The

. fastness of the dyeings thereon against washing and light is likewise not inferior to those on wool owing to the insolubility and chemical resistance of the polymerization products.

The following examples serve to illustrate the invention:

Example 1 merization and may be about 60-100 cc.` This,

animalizing solution is again allowed to stand for 24 hours at room temperature for the purpose of further polymerization. Of this iinished solution 150 cc. are added to 5 liters of viscose and the whole is well emulsied. 'After de-aeration the viscose is spun. The corresponding proportion of animalizing solution may alternatively be added to the spinning solution on its way to the spinning nozzle. The animalized threads have a strong ailinity for acid wool dyestuifs, very good fastness to washing and especially good fastness to light in the case of after-chroming dyestuffs. Example '2 To a mixture of 400 cc. of benzene and -cc. of carbon disulilde there are added gradually cc. of phenylisocyanate. There are then added cautiously drop by drop at 40 C. in a reflux apparatus 100 cc. of ethyleneimine (98 per cent strength).

The condensation product is allowed to stand for 72 hours for further polymerization. Of this animalizing solution 100 cc. are stirred into 5 liters of viscose, which is thenispun. The fibers dyed with wool dyestuffs, for instance metabenzene solution of the artiilcial resin, then chrome Red 5 G. Anthralan Yellow, Supramine Red B, Chrome Yellow A, fast Mordant Blue B. exhibit very good fastness to and Derspiration. The fastness to light of the fibers is very good, especially in the case oi after-chrom- 5 ing and meta-chrome dyestuffs.

Example 3 To a solution of 200 cc. of benzene and 100 cc. of ethyleneimine (98 per cent strength) are added at 40 C. through a dropping funnel 100 cc. of carbon disulfide. The solution is allowed to stand for 24 hours and then at 40 C. 125 cc. of phenylisocyanate are added by drops. The resinous polymerizate is left i'or 24 hours at room temperature for further polymerization. It is soluble in ethylenechlorhydrin and in benzylalcohol. 100 cc. of the 'animalizing solution dissolved in a little benzyl alcohol are thoroughly emulsiiled in 5 liters of viscose and the mass is spun in known manner. Finished threads have a strong amnity for acid wool dyestuifs. After dyeing they are thoroughly fast to washing. The fastness to light of the bers dyed with after-chromlng dyestus is very good.

Example 4 Example 5 cc. of N-benzylethyleneimine in 300 cc. of benzene are cautiously caused to react at 40 C.l with 50 cc. of carbon disulfide. The whole is allowed to stand for 24 hours at room temperature and then at 40 C. and under reflux there are added 60 cc. of a-naphthylisocyanate. The resin solutionl thus obtained is allowed to stand for 3 days while warm for polymerization and may then be used for animalizing ilbers. For example, cotton fabric may be saturated with a squeezed between calender rollers and dried. If desired, the resin is used in the form of an aqueous emulsion for preparing the fabric.

In the foregoing examples carbon disulilde may be replaced by the above-named sulfur compounds, while ethyleneimlne may be `replaced by any oi'- the above-named alkyleneimines, and phenylisocyanate by any of the ,above-named isocyanates.

We claim:

1. Textile materials capable of being dyed with acid wool dyestuifs in the same manner as wool, comprising a film-l or fiber-forming organic polymer incapable perse of being dyed by acid dyes, said nlmor ber-forming polymer containing ilnely distributed therein the resinous product of'a Joint polymerization of the following three resin components: 1. an alkylene imine, 2. a suliur compound selected from the group consisting of carbondisulilde, carbonyl sulfide. thiophosgene and sulfur chloride, and 3. a compoimd selected from the group consisting of arylthiocyanates and arylisothiocyanates.

2. Textile materials capable of being dyed by acid wool dyestuil's in the same manner as wool, Il

comprising a filmor fiber-forming organic polymerization of the following three resin constimer incapable per se of 'being dyed by acid dyes, tuents: 1.' ethyleneimine, 2. carbondisuliide, and said lnior fiber-forming polymer containing 3. phenylisocyanate.

Iinely distributed therein the'resinous product of 4. Textile materials capable of being dyed by 5 a joint polymerization of the following three resacid wool dyestuifs in the same manner as wool in components: 1. ethyleneimine, 2. carbon disulcomprising cotton fibers impregnated with the de, and 3. phenylisocyanate. resinous product of the joint polymerization of 3. Textile materials capable of being dyed by the following three constituents: 1. ethyleneiacid wool dyestus in the same manner as wool mine, 2. carbondisulde, and 3. phenylisocyanate.

10 comprising cellulose hydrate and iinely dispersed PAUL ESHSELMANN. lo

therein the resinous product of the joint poly- JOSEF DUSING. 

